Porous dielectric material with improved pore surface properties for electronics applications

ABSTRACT

This invention provides an improved porous structure for semiconductor devices and a process for making the same. This process may be applied to an existing porous structure 28, which may be deposited, for example, between patterned conductors 24. The process may include baking the structure in a reducing atmosphere, preferably a forming gas, to dehydroxylate the pore surfaces. The process may include baking the structure in a halogen-containing atmosphere to bond halogens to the pore surfaces. It has been found that a porous structure treated in such a manner generally exhibits improved dielectric properties relative to an untreated sample.

This is a continuation of application Ser. No. 08/263,572, filed Jun.23, 1994, now U.S. Pat. No. 5,504,042.

CROSS-REFERENCE TO RELATED APPLICATIONS

The following co-assigned U.S. patent applications are herebyincorporated herein by reference:

    __________________________________________________________________________    TI Case                                                                            Serial No                                                                          Filing Date                                                                         Inventor                                                                             Title                                                  __________________________________________________________________________    TI-18941                                                                           08/247195                                                                          5/20/94                                                                             Gnade et al                                                                          A Low Dielectric Constant                                                     Material For Electronics                                                      Applications                                           TI-19072                                                                           08/246432                                                                          5/20/94                                                                             Havemann et al                                                                       Interconnect Structure with an                                                Integrated Low Density                                                        Dielectric                                             TI-19253                                                                           --   5/27/94                                                                             Havemann et al                                                                       Two-Step Metal Etch Process                                                   For Selective Gap Fill of                                                     Submicron Interconnects and                                                   Structure For Same                                     TI-19178                                                                           --   6/07/94                                                                             Gnade et al                                                                          Porous Composites as a Low                                                    Dielectric Constant Material                                                  for Electronics Applications                           __________________________________________________________________________

FIELD OF THE INVENTION

This invention relates generally to the fabrication of dielectrics onsemiconductor devices, and more particularly to methods for reducingcapacitive coupling on a semiconductor device using electricalinsulators made of porous dielectric materials.

BACKGROUND OF THE INVENTION

Semiconductors are widely used in integrated circuits for electronicdevices such as computers and televisions. These integrated circuitstypically combine many transistors on a single crystal silicon chip toperform complex functions and store data. Semiconductor and electronicsmanufacturers, as well as end users, desire integrated circuits whichcan accomplish more in less time in a smaller package while consumingless power. However, many of these desires are in opposition to eachother. For instance, simply shrinking the feature size on a givencircuit from 0.5 microns to 0.25 microns can increase power consumptionby 30%. Likewise, doubling operational speed generally doubles powerconsumption. Miniaturization also generally results in increasedcapacitive coupling, or crosstalk, between conductors which carrysignals across the chip. This effect both limits achievable speed anddegrades the noise margin used to insure proper device operation.

One way to diminish power consumption and crosstalk effects is todecrease the dielectric constant of the insulator, or dielectric, whichseparates conductors. Probably the most common semiconductor dielectricis silicon dioxide, which has a dielectric constant of about 3.9. Incontrast, air (including partial vacuum) has a dielectric constant ofjust over 1.0. Consequently, many capacitance-reducing schemes have beendevised to at least partially replace solid dielectrics with air.

U.S. Pat. No. 5,103,288, issued to Sakamoto, on Apr. 7, 1992, describesa multilayered wiring structure which decreases capacitance by employinga porous dielectric with 50% to 80% porosity (porosity is the percentageof a structure which is hollow) and pore sizes of roughly 5 nm to 50 nm.This structure is typically formed by depositing a mixture of an acidicoxide and a basic oxide, heat treating to precipitate the basic oxide,and then dissolving out the basic oxide. Dissolving all of the basicoxide out of such a structure may be problematic, because small pocketsof the basic oxide may not be reached by the leaching agent.Furthermore, several of the elements described for use in the basicoxides (including sodium and lithium) are generally consideredcontaminants in the semiconductor industry, and as such are usuallyavoided in a production environment. Creating only extremely small pores(less than 10 nm) may be difficult using this method, yet thisrequirement will exist as submicron processes continue to scale towardsa tenth of a micron and less.

Another method of forming porous dielectric films on semiconductorsubstrates (the term "substrate" is used loosely herein to include anylayers formed prior to the conductor/insulator level of interest) isdescribed in U.S. Pat. No. 4,652,467, issued to Brinker et al., on Mar.24, 1987. This patent teaches a sol-gel technique for depositing porousfilms with controlled porosity and pore size (diameter), wherein asolution is deposited on a substrate, gelled, and then cross-linked anddensified by removing the solvent through evaporation, thereby leaving aporous dielectric. This method has as a primary objective thedensification of the film, which teaches away from low dielectricconstant applications. Dielectrics formed by this method are typically15% to 50% porous, with a permanent film thickness reduction of at least20% during drying. The higher porosities (e.g. 40%-50%) can only beachieved at pore sizes which are generally too large for suchmicrocircuit applications. These materials are usually referred to asxerogels, although the final structure is not a gel, but an open-pored(the pores are generally interconnected, rather than being isolatedcells) porous structure of a solid material.

SUMMARY OF THE INVENTION

The present invention provides methods for modifying surface propertiesof porous dielectric layers on semiconductor devices and porousstructures with modified pore surface chemistry. It is recognized hereinthat extremely porous dielectric layers (porosity generally greater than50% and preferably greater than 75%) may provide a low dielectricconstant insulation for decreasing unwanted capacitive coupling onsemiconductor devices. A heretofore unrecognized problem with suchporous layers is the degree to which the surface composition of theinternal pore surfaces may affect dielectric properties such asdielectric constant, resistivity, dielectric breakdown voltage, anddielectric loss factor (a measure of the relative energy consumed by thedielectric of a capacitor during charging).

It has now been recognized that significant changes in theaforementioned dielectric properties may be effected by removing and/orreplacing surface groups (particularly hydroxyl groups) initiallypresent on the pore surfaces of porous dielectrics. The dielectricproperties of the solid phase of such porous materials appear to begreatly affected by surface species. Because of high surface area(roughly 1000 m² g⁻¹ is typical of porous dielectrics), it is hereinrecognized that highly polar species (e.g. hydroxyl groups) may affectdielectric properties greatly (the dielectric constant of water, whichconsists of hydroxyl groups bound to hydrogen, is 78). For example, afully hydroxylated porous dielectric (1000 m² g⁻¹ surface area) maycontain roughly 14 wt % surface hydroxyls, and an additional 6 wt % ofbound water attached to these hydroxyls.

Others have recognized other detrimental effects (e.g. foaming, infraredabsorption) of high quantities of hydroxyl surface groups for sinteredgels and other silica products such as those used in the fiber opticsindustry. As such, techniques such as high temperature dehydroxylation,chemical dehydroxylation through surface reaction withhalogen-containing gasses, or combinations of these techniques have beendeveloped. It is recognized herein that techniques applicable tosintered glass, solid substrates, and the like may be unsuited for aporous semiconductor dielectric, where compatibility with other layersof the device (such as aluminum-containing conductors) and preservationof the porous structure are generally important considerations. Inaccordance with the present invention, methods described herein may beused to remove surface groups from a porous dielectric, preferablybefore creating non-porous layers on top of the porous layer. Inparticular, methods of dehydroxylation are presented which arechemically and thermally compatible with semiconductor fabrication.These methods may be used to improve one or more of the aforementioneddielectric properties without significant change to the mechanicalproperties of a porous dielectric or breakdown of other deviceconstructs.

The present invention provides a method of heat treating a porousdielectric formed on a semiconductor device for the removal of surfacegroups (including, preferably, at least 70%, and more preferably, atleast 90% of surface hydroxyl (OH) groups). The method may comprise,before capping the porous dielectric layer, baking the device at one ormore temperatures in the range of 100° C. to 490° C. (preferably 300° C.to 450° C.). The method may further comprise carrying out the bakingstep in a reducing atmosphere, preferably an H₂ -containing -containing,substantially oxygen-free atmosphere, and more preferably in a forminggas (approximately 10% H₂, 90% N₂ by volume). Alternately, or inaddition to the forming gas step, the method may comprise carrying outthe baking step in an atmosphere which contains fluorine compounds (e.g.ammonium fluoride, hydrogen fluoride, fluorine gas) which react with thehydroxyl groups on the surface. Note that while chlorine compounds (e.g.carbon tetrachloride, silicon tetrachloride, chlorine gas) might beusable, they are preferably avoided as they may cause corrosion problemsin aluminum conductors. The method may further comprise maintaining theatmosphere at or below ambient pressure during the baking step(preferably at ambient pressure). Preferably, the baking process reducesthe thickness of the porous dielectric by less than 5%.

The present invention provides a structure for semiconductor devices,which may comprise a porous dielectric layer with at least 20% porosity(preferably at least 50% porosity) deposited at least partially betweenpatterned conductors on a substrate. The porous dielectric may containless than 1.5 OH groups/nm² (preferably less than 0.5 OH groups/nm²).The porous dielectric may contain fluorine-containing surface groups,preferably in a concentration of greater than 0.8 groups/nm². The devicemay further comprise a substantially solid cap layer deposited over theporous dielectric layer.

BRIEF DESCRIPTION OF THE DRAWINGS

This invention, including various features and advantages thereof, canbe best understood by reference to the following drawings, wherein:

FIGS. 1A-1D show cross-sections of a portion of a semiconductor device,illustrating several steps in the application of an embodiment of theinvention to a typical device; and

FIGS. 2A and 2B contain Fourier Transform Infrared (FTIR) transmissionspectra of the same dielectric layer, respectively before and afterheating in a forming gas.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Typical embodiments of the invention are described with a porousdielectric method of depositing a solution, gelling it on the substrate,surface modification, and drying to form a porous dielectric from thewet gel. All steps detailed for this process may not be required in agiven embodiment. Furthermore, materials may be substituted in severalof the steps to achieve various effects, and processing parameters suchas times, temperatures, pressures, and relative concentrations ofmaterials may be varied over broad ranges. In any case, another methodwhich produces a similar porous dielectric layer could be substitutedfor the described method.

As an introduction, FIGS. 1A-1D illustrate a semiconductor structure atseveral steps in the formation of a dielectric layer. In FIG. 1A, threepatterned conductors 24 (e.g. of aluminum alloyed with a small amount ofcopper) are shown formed on an insulating layer 22 (e.g. SiO₂), whichmay contain vias or through holes (not shown) for providing electricalcontact between conductors 24 and lower layers of the device. In FIG.1B, a gel precursor solution (some of which are described in detail inthe specific chemical examples) is shown after disposition and gellingin the gaps between conductors 24 to form a wet gel sublayer 26. Themethod of application may be, for example, a spin-on technique in acontrolled atmosphere which limits solvent evaporation. The precursormay be prepared, for example, by the following 2-step process. First,TEOS stock, a mixture of tetraethylorthosilicate (TEOS), ethanol, water,and HCl, in the approximate molar ratio 1:3:1:0.0007, is prepared bystirring these ingredients under constant reflux at 60 degrees C. for1.5 hours. Secondly, 0.05M ammonium hydroxide is added to the TEOSstock. 0.1 ml for each ml of TEOS stock. After the solution is appliedto the wafer, care should be taken to insure that the thin film does notdry prematurely; preferably, the wafer containing the solution/gelgenerally remains immersed either in liquid or in a saturated atmosphereat all times prior to the drying stage. The precursor solution maypreferably be gelled on the substrate, a process which typically takesfrom 1 minute to 12 hours, depending on the solution and method ofgelling. The wet gel can be allowed time to age, generally about a day(although it may be much shorter), at one or more controlledtemperatures. Gelation and aging may preferably be accomplished byletting the device sit in a saturated ethanol atmosphere forapproximately 24 hours at about 37 degrees C.

Next, the water may be removed from the wet gel, preferably by immersingthe wafer in pure ethanol. In this example, a surface modification stepis performed on the wet gel, replacing a substantial number of themolecules on the pore walls with those of another species. Surfacemodification may be performed, for example, by immersing the wafer in ahexane solution containing about 10% by volume trimethylchlorosilane(TMCS). This surface modification typically replaces reactive surfacegroups such as hydroxyls and alkoxyls with more stable surface groupssuch as methyl groups, thereby controlling undesirable condensationreactions (and shrinkage effects) during gel drying. It has beendiscovered that by controlling the percentage of reactive surface groupsreplaced during the surface modification, the final shrinkage may beadjusted from the large shinkage typical of an unmodified xerogel (withuncontrolled shrinkage) to a shrinkage of only a few percent, heretoforeonly achievable with a supercritical aerogel technique. Typically,approximately 30% of the reactive surface groups must be replaced tosubstantially alleviate densification. Furthermore, the replacementsurface species may be chosen because of its wetting properties incombination with specific pore fluids; the surface modification mayresult in a pore fluid contact angle closer to 90 degrees, which isdesirable because of a corresponding decrease in capillary forces in thegel structure during drying. It is believed that the surfacemodification prevents surface condensation reactions, and may alsoreduce capillary pressure by changing pore fluid contact angle, therebyallowing pores in the surface modified gel to better survive drying.

After a brief reaction time, the unreacted surface modification compoundis usually removed by immersing the wafer in an aprotic solvent (e.g.acetone, hexane) and allowing excess solvent to drain. After thissolvent exchange, solvent is finally allowed to evaporate from wet gel26. This may produce a structure similar to that of FIG. 1C, whichillustrates the dried gel now forming a porous dielectric layer 28, andalso illustrates the few percent shrinkage typical of this method (thedried porous film thickness is only slightly less than the wet gelthickness).

Finally, depending on the porosity and thickness selected for sublayer28, it may be preferable to follow the drying process with deposition ofnon-porous dielectric layer 30, as shown in FIG. 1D. This layer maypreferably be composed of silicon dioxide deposited by a chemical vapordeposition (CVD) technique. Preferably, the dehydroxylation methodspresented in this invention are carried out before deposition ofnon-porous dielectric layer 30.

As an example, one embodiment of the method of the invention isdiscussed herein as applied to a wafer containing a porous layerdeposited over a silicon substrate, with the porous layer having anapproximate thickness of 1.5 microns. The measured porosity of thesample is 84%, and it is believed that about 65% of the surface OHgroups originally present on the wet gel were replaced with methylgroups prior to drying.

FIG. 2A, obtained by FTIR spectroscopy, shows the transmittance of theporous dielectric of the wafer described above, as a function ofwavenumber. Specific molecular structures absorb energy at discretewavenumbers, forming a signature which is generally unique to astructure. Therefore, the absorption peaks (which actually peakdownwards in FIG. 2A, since the graph shows transmittance) indicate thepresence of various molecular structures in the porous dielectric.Several peaks are labelled in this figure, including CH₃ and Si--CH₃peaks, which indicate that the surface modification does place methylgroups on the pore walls, and a large Si--O peak corresponding to thematerial which forms most of the porous dielectric. Note also the Si--OHpeak, shown as a knee on the Si--O peak, indicating that some OH groupsare still present on the pore walls. Because the Si--O and Si--OH bandsoverlap, both contribute to the 18% transmittance peak at around 1050wavenumbers.

Measurements taken on the sample porous dielectric indicate a dielectricconstant of about 1.34, which is almost 10% higher than the theoreticalvalue for a 16% dense structure where the solid phase has the dielectricconstant of bulk silica. Surprisingly, other measurements indicatebreakdown voltage and leakage (due to low resistivity) far inferior tothose of bulk silica. It is believed that these discrepancies areprimarily due to the effect of surface species, which are shown in FIG.2A to be comprised substantially of hydroxyl and methyl groups.Theoretically, a fully hydroxylated silica surface contains about 4.9 OHgroups/nm². It is recognized herein that for dielectric purposes, it maybe desirable to reduce this concentration below 1.5 OH groups/nm², andpreferably below 0.5 OH groups/nm².

Techniques commonly found in other industries for removing hydroxyl (seeSol-Gel Science: The Physics and Chemistry of Sol-Gel Processing,Chapter 10, by C. J. Brinker et al, Academic Press, 1990) groups from adried gel (known as dehydroxylation) generally teach that hightemperatures (usually at least 700 to 800 C.) are required for effectiveremoval. Furthermore, other known applications of dried silica gelsgenerally teach that densification, or sintering, of the gel isdesirable. However, the common use of aluminum alloy conducting layersin the semiconductor industry generally requires that no processingtemperatures (including heating for dehydroxylation of porousdielectrics) exceed about 450 C. after metal deposition. In addition,sintering of a dried gel deposited for its low dielectric constantdefeats the original purpose of the deposition.

The present invention includes a group of dehydroxylation techniqueswhich may be applied to a semiconductor device during fabrication, attemperatures generally at or below 490 C., and at a range of pressuresfrom vacuum to near-critical, with atmospheric pressure being preferabledue to ease of handling and compatibility with previous porous layers.These techniques may either remove a portion of the surface groupsentirely (in which case it is believed that highly strained Si--O--Sibonds may be formed on the pore surfaces), or replace the surfacechemistry with other, preferably less polar systems (such as hydrogen orfluorine).

In an example of one embodiment of the invention, a structure (e.g. thatof the example wafer) is placed in a forming gas atmosphere comprised of10 vol % H₂, 90 vol % N₂ at atmospheric pressure, and baked at 450 C.for approximately 30 minutes. The resulting structure is slightlydensified, with a measured porosity of 80% for the initially 84% porousexample. It is believed that the observed densification is due to thecreation of strained Si--O--Si bonds at neighboring surface sites whereOH groups and/or methyl groups are removed. FIG. 2B shows an FTIRtransmission spectra for the porous dielectric of the example, afterbaking in a forming gas. Surprisingly, peaks corresponding to surfacespecies on FIG. 2A are either sharply reduced or non-existent in FIG.2B. In particular, the Si--OH knee on the Si--O peak is gone, and thecombined Si--O, Si--OH transmission minima shows a 40% transmission,where before there was 18% transmission. Also, the CH₃ peak, whichpreviously showed 92% transmission, now show 98% transmission. It isbelieved that the forming gas treatment removes over 90% of the surfacehydroxyls and 75% of the methyl groups on a sample of this type.

An additional benefit of the forming gas treatment is increasedhydrophobicity. As disclosed previously, the surface modified xerogelsare inherently hydrophobic. Experiments performed on the porousstructure before and after the forming gas treatment show increasedhydrophobicity as a result of the treatment.

The invention may also comprise the steps of placing the device in anatmosphere which contains fluorine compounds (e.g. ammonium fluoride,hydrogen fluoride, fluorine gas) which react with the hydroxyl groups onthe surface. These methods also are generally limited to temperatures of450 C., and therefore may not provide the same level of dehydroxylationprovided by the forming gas technique. However, an additional advantageof at least partially fluorinating the porous surface may beoleophobicity. The resulting structure may not only resist penetrationby water, but by oils and alcohols also. This allows wet depositiontechniques to be performed directly over the porous layer, since such astructure resists wetting by most chemicals.

The following table provides an overview of some embodimentscross-referenced to the drawings.

    __________________________________________________________________________          Preferred or                                                            Drawing                                                                             Specific                                                                Element                                                                             Examples Generic Term                                                                          Other Alternate Examples                               __________________________________________________________________________    22    Previous Insulating layer                                                                      Previously-formed layers of a                                interlayer       semiconductor device, substrate                              dielectric                                                              24    AlCu alloy                                                                             Conductors                                                                            Al, Cu, Mo, W, Ti, and alloys of                             and/or refractory                                                                              these                                                        metal            Polysilicon, silicides, nitrides,                                             carbides                                               26    TEOS stock                                                                             Precursor                                                                             Solution of particulate or colloidal                                  solution                                                                              silicon, germanium, titanium,                                                 aluminum silicate                                                             ratioed TEOS/MTEOS                                                            (methyltriethoxysilane) stock,                                                ratioed TEOS/BTMSE                                                            (1,2-Bis(trimethoxysilyl)ethane)                                              stock                                                  28    Surface-modified                                                                       Porous  Supercritically-dried aerogel, other                         dried gel                                                                              dielectric                                                                            fine-pored porous dielectrics                                         sublayer                                                       30    Silicon dioxide                                                                        Non-porous                                                                            Other oxides, B or P-doped SiO.sub.2,                                 dielectric layer                                                                      silicon nitride, silicon oxynitride                                           Parylene, polyimides, organic-                                                containing oxide                                       __________________________________________________________________________

The invention is not to be construed as limited to the particularexamples described herein, as these are to be regarded as illustrative,rather than restrictive. The invention is intended to cover allprocesses and structures which do not depart from the spirit and scopeof the invention. For example, the invention is primarily directed toimproving dielectric properties of a porous layer, and such a layer maybe used in many semiconductor device structures other than the specificstructures shown herein. Properties of some of the specific examples maybe combined without deviating from the nature of the invention.

What is claimed is:
 1. A method of constructing a semiconductor device,said method comprising:providing a substrate containing an uncappedporous dielectric layer having a first thickness and having a porositygreater than 50% and an average pore diameter between 2 and 80 nm; andheating said substrate to one or more temperatures between 100° C. and450° C. in an atmosphere comprising at least one fluorine compound,thereby at least partially fluorinating pore surfaces in said porousdielectric while reducing said first thickness by less than 5%; wherebysaid porous dielectric is rendered both hydrophobic and oleophobic. 2.The method of claim 1, further comprising depositing a substantiallysolid cap layer over said porous dielectric.
 3. The method of claim 1,further comprising depositing a substantially solid cap layer over saidporous dielectric by a wet deposition technique.
 4. The method of claim1, wherein said fluorine compound is selected from the group consistingof: ammonium fluoride, hydrogen fluoride, fluorine gas, and combinationsthereof.
 5. The method of claim 1, wherein said heating said substratestep is carried out at one or more temperatures between 300° C. and 450°C.